U.S. patent application number 14/929970 was filed with the patent office on 2017-05-04 for polydimethylsiloxane cross-linking materials.
The applicant listed for this patent is International Business Machines Corporation. Invention is credited to Brandon M. Kobilka, Joseph Kuczynski, Phillip V. Mann, Jason T. Wertz.
Application Number | 20170121469 14/929970 |
Document ID | / |
Family ID | 58634580 |
Filed Date | 2017-05-04 |
United States Patent
Application |
20170121469 |
Kind Code |
A1 |
Kobilka; Brandon M. ; et
al. |
May 4, 2017 |
POLYDIMETHYLSILOXANE CROSS-LINKING MATERIALS
Abstract
In an example, a process of forming a polymeric material
includes forming a mixture that includes a polydimethylsiloxane
(PDMS) material and a pentaerythritol cross-linking material. The
process also includes forming a cross-linked PDMS material via a
chemical reaction of the pentaerythritol cross-linking material and
the PDMS material.
Inventors: |
Kobilka; Brandon M.;
(Tucson, AZ) ; Kuczynski; Joseph; (North Port,
FL) ; Mann; Phillip V.; (Rochester, MN) ;
Wertz; Jason T.; (Pleasant Valley, NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
International Business Machines Corporation |
Armonk |
NY |
US |
|
|
Family ID: |
58634580 |
Appl. No.: |
14/929970 |
Filed: |
November 2, 2015 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 77/44 20130101;
C08G 77/48 20130101 |
International
Class: |
C08J 3/24 20060101
C08J003/24 |
Claims
1. A process of forming a polymeric material, the process
comprising: forming a mixture that includes a polydimethylsiloxane
(PDMS) material and a pentaerythritol cross-linking material; and
forming a cross-linked PDMS material via a chemical reaction of the
pentaerythritol cross-linking material and the PDMS material.
2. The process of claim 1, wherein the pentaerythritol
cross-linking material includes bio-renewable pentaerythritol.
3. The process of claim 1, wherein the PDMS material includes a
hydridefunctionalized PDMS material, and wherein the chemical
reaction includes a condensation cure reaction using dibutyltin
dilaurate (DBDTL) as a catalyst.
4. of claim 1, wherein the PDMS material includes an
alkoxyfunctionalized PDMS material, and wherein the chemical
reaction includes a condensation cure reaction using dibutyltin
dilaurate (DBDTL) as a catalyst.
5. The process of claim 4, wherein the alkoxy-functionalized PDMS
material includes a methoxy-functionalized PDMS material.
6. A process of forming a polymeric material, the process
comprising: forming a mixture that includes a polydimethylsiloxane
(PDMS) material and a pentaerythritol-derived cross-linking
material; and forming a cross-linked PDMS material via a chemical
reaction of the pentaerythritol-derived cross-linking material and
the PDMS material.
7. The process of claim 6, wherein the pentaerythritol-derived
cross-linking material is formed from bio-renewable pentaerythritol
and a second bio-renewable material.
8. The process of claim 6, wherein the pentaerythritol-derived
cross-linking material includes multiple acetate groups.
9. The process of claim 8, wherein the PDMS material includes a
hydroxyfunctionalized PDMS material.
10. The process of claim 6, wherein the pentaerythritol-derived
cross-linking material includes multiple vinyl groups.
11. The process of claim 10, wherein the chemical reaction includes
a radical cure reaction using a peroxide initiator.
12. The process of claim 10, wherein the chemical reaction includes
an addition cure reaction using a platinum catalyst.
13. The process of claim 6, wherein the pentaerythritol-derived
cross-linking material includes multiple thiol groups.
14. The process of claim 12, wherein the PDMS material includes a
vinylfunctionalized PDMS material, and wherein the chemical
reaction includes a thiol-ene cure reaction.
15. A cross-linked polydimethylsiloxane (PDMS) material that is
cross-linked using a pentaerythritol-based cross-linking material
that is formed from bio-renewable pentaerythritol.
16. The cross-linked PDMS material of claim 15, wherein the
pentaerythritol based cross-linking material includes the
bio-renewable pentaerythritol.
17. The cross-linked PDMS material of claim 15, wherein the
pentaerythritol based cross-linking material is formed via a
chemical reaction of the bio-renewable pentaerythritol and a second
material, the second material including bio-renewable acetic acid
or an acetic anhydride that is derived from bio-renewable acetic
acid.
18. The cross-linked PDMS material of claim 15, wherein the
pentaerythritol based cross-linking material is formed via a
chemical reaction of the bio-renewable pentaerythritol and
bio-renewable acrylic acid.
19. The cross-linked PDMS material of claim 15, wherein the
pentaerythritolbased cross-linking material is formed via a
chemical reaction of the bio-renewable pentaerythritol and an allyl
bromide that is derived from a bio-renewable allyl alcohol.
20. The cross-linked PDMS material of claim 15, wherein the
pentaerythritol based cross-linking material is formed via a
chemical reaction of the bio-renewable pentaerythritol and ethyl
mercaptoic acid, wherein the ethyl mercaptoic acid is formed from a
bio-renewable acrylic acid.
Description
I. FIELD OF THE DISCLOSURE
[0001] The present disclosure relates generally to
polydimethylsiloxane (PDMS) cross-linking materials.
II. BACKGROUND
[0002] Polydimethylsiloxane (PDMS) is among the widely used
silicon-based polymers, and the most widely used organic
silicon-based polymer. PDMS materials have a wide range of
applications including contact lenses, medical devices, soft
lithography processes, shampoos, caulking, and lubricants (among
other alternatives). One reason for the wide-ranging applications
for PDMS materials is the variety of ways in which the properties
of PDMS may be controlled through polymer cross-linking. By
employing PDMS and small organic molecules with different organic
functional groups, many possibilities exist for different PDMS
materials to be cross-linked in different ways.
III. SUMMARY OF THE DISCLOSURE
[0003] According to an embodiment, a process of forming a polymeric
material is disclosed. The process includes forming a mixture that
includes a PDMS material and a pentaerythritol cross-linking
material. The process also includes forming a cross-linked PDMS
material via a chemical reaction of the pentaerythritol
cross-linking material and the PDMS material.
[0004] According to another embodiment, a process of forming a
polymeric material is disclosed. The process includes forming a
mixture that includes a PDMS material and a pentaerythritol-derived
cross-linking material. The process also includes forming a
cross-linked PDMS material via a chemical reaction of the
pentaerythritol-derived cross-linking material and the PDMS
material.
[0005] According to another embodiment, a cross-linked PDMS
material is disclosed. The cross-linked PDMS material is
cross-linked using a pentaerythritol-based cross-linking material
that is formed from bio-renewable pentaerythritol.
[0006] One advantage of the present disclosure is the ability to
form cross-linked PDMS materials using pentaerythritol-based
cross-linking materials, such as a bio-renewable pentaerythritol
cross-linking material or a pentaerythritol-based cross-linking
material derived from bio-renewable pentaerythritol. Utilizing
bio-renewable pentaerythritol (or derivatives of bio-renewable
pentaerythritol) as a cross-linking material may increase the
bio-renewable content of a cross-linked PDMS material, for use in
various applications.
[0007] Features and other benefits that characterize embodiments
are set forth in the claims annexed hereto and forming a further
part hereof. However, for a better understanding of the
embodiments, and of the advantages and objectives attained through
their use, reference should be made to the Drawings and to the
accompanying descriptive matter.
IV. BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 is a chemical reaction diagram illustrating the
preparation of a first cross-linked PDMS material using
pentaerythritol (PE) as a cross-linking material, according to one
embodiment;
[0009] FIG. 2 is a chemical reaction diagram illustrating the
preparation of a second cross-linked PDMS material using PE as a
cross-linking material, according to one embodiment;
[0010] FIG. 3 is a chemical reaction diagram illustrating the
preparation of a third cross-linked PDMS material using a PE-based
cross-linking material, according to one embodiment;
[0011] FIG. 4 is a chemical reaction diagram illustrating the
preparation of a fourth cross-linked PDMS material using a PE-based
cross-linking material, according to one embodiment;
[0012] FIG. 5 is a chemical reaction diagram illustrating the
preparation of a fifth cross-linked PDMS material using a PE-based
cross-linking material, according to one embodiment;
[0013] FIG. 6 is a chemical reaction diagram illustrating the
preparation of a sixth cross-linked PDMS material using a PE-based
cross-linking material, according to one embodiment;
[0014] FIG. 7 is a chemical reaction diagram illustrating the
preparation of a seventh cross-linked PDMS material using a
PE-based cross-linking material, according to one embodiment;
and
[0015] FIG. 8 is a chemical reaction diagram illustrating the
preparation of an eighth cross-linked PDMS material using a
PE-based cross-linking material, according to one embodiment.
V. DETAILED DESCRIPTION
[0016] The present disclosure describes cross-linked PDMS materials
that are cross-linked using PE-based cross-linking materials and
processes of forming cross-linked PDMS materials using PE-based
cross-linking materials. As further described herein, in some
cases, PE (e.g., bio-renewable PE) may be used as a cross-linking
material. In other cases, a PE-derived material (e.g., a PE-based
material derived from bio-renewable PE) may be used as the
cross-linking material. Utilizing bio-renewable PE (or derivatives
of bio-renewable PE) as a cross-linking material may increase the
bio-renewable content of a cross-linked PDMS material, for use in
various applications.
[0017] The PE-based cross-linkers of the present disclosure may be
applied to PDMS for different applications. In some cases, curing
may be performed during processing of a desired material, with a
completely cross-linked polymer. In other cases, the cross-linkers
may be mixed with PDMS but left in a partial or uncross-linked
state that can be left to cross-link upon addition to the PDMS for
a particular desired application (e.g., a caulking or coating
application, among other alternatives).
[0018] In a particular embodiment, the PE cross-linking material
includes bio-renewable PE. In some cases, bio-renewable PE may be
commercially available. Alternatively, bio-renewable PE may be
synthesized using various approaches. As an example, bio-renewable
PE may be formed from a biomass source, such as lignin, wood pulp,
or a combination thereof. As another example, bio-renewable PE may
be formed via an alcohol-chemical route. To illustrate, ethanol may
be oxidized to form acetaldehyde, an intermediate for the
production of PE. As a further example, one or more bio-renewable
PE esters may be hydrolyzed to form bio-renewable PE. As yet
another example, shorter chain fatty acids may be used to form PE
esters (which may be hydrolyzed to form bio-renewable PE). It will
be appreciated that numerous methods may be employed to form a
bio-renewable PE cross-linking material and/or a PE-derived
bio-renewable cross-linking material. Further, the PE-derived
cross-linking materials described herein may be formed from PE,
bio-renewable PE, a second bio-renewable material (or materials),
or a combination thereof.
[0019] Referring to FIG. 1, a chemical reaction diagram 100
illustrates the preparation of a cross-linked PDMS material using
PE (e.g., bio-renewable PE) as a cross-linking agent, according to
one embodiment. In the example of FIG. 1, a mixture may be formed
that includes a PDMS material (e.g., a hydride-functionalized
siloxane) and PE cross-linking material. The cross-linked PDMS
material illustrated in FIG. 1 may be formed via a chemical
reaction (e.g., a condensation cure reaction) of the PE
cross-linking material and the PDMS material. In the example of
FIG. 1, dibutyltin dilaurate (DBTDL) may be used as a catalyst for
the chemical reaction.
[0020] FIG. 1 illustrates an example in which all four hydroxyl
groups of a single PE molecule are used as cross-linking sites.
Depending on the reaction conditions, all four hydroxyl groups can
be used to cross-link PDMS or, by controlling the reaction
conditions, catalyst loading, and stoichiometry, a fraction of the
hydroxyl groups (e.g., less than four hydroxyl groups per PE
molecule, on average) can be used to cross-link PDMS. This may
enable more control of the mechanical properties of the final
polymer.
Prophetic Example: Synthesis of a Cross-Linked PDMS Material Using
PE (e.g., Bio-Renewable PE) as a Cross-Linking Material
[0021] As a prophetic example, a hydride-functionalized siloxane
may be blended with a PE cross-linker (about 1-20% w/w) and
catalyst (DBDTL in this case, 0.1%-2.0% w/w) and mixed. The mixture
may be applied to molds or coated onto a substrate and cured for
times and temperatures as appropriate for desired applications.
[0022] Thus, FIG. 1 illustrates an example of the preparation of a
cross-linked PDMS material using PE as a cross-linking material.
When the PE cross-linking material is derived from renewable
resources, the bio-renewable content of a resulting cross-linked
PDMS material may be increased.
[0023] Referring to FIG. 2, a chemical reaction diagram 200
illustrates the preparation of a cross-linked PDMS material using
PE (e.g., bio-renewable PE) as a cross-linking agent, according to
one embodiment. In the example of FIG. 2, a mixture may be formed
that includes a PDMS material (e.g., an alkoxy-functionalized
siloxane, such as a methoxy-functionalized siloxane) and PE
cross-linking material. The cross-linked PDMS material illustrated
in FIG. 2 may be formed via a chemical reaction (e.g., a
condensation cure reaction) of the PE cross-linking material and
the PDMS material. In the example of FIG. 2, DBTDL may be used as a
catalyst for the chemical reaction.
[0024] FIG. 2 illustrates an example in which all four hydroxyl
groups of a single PE molecule are used as cross-linking sites.
Depending on the reaction conditions, all four hydroxyl groups can
be used to cross-link PDMS or, by controlling the reaction
conditions, catalyst loading, and stoichiometry, a fraction of the
hydroxyl groups (e.g., less than four hydroxyl groups per PE
molecule, on average) can be used to cross-link PDMS. This may
enable more control of the mechanical properties of the final
polymer.
Prophetic Example: Formation of a Cross-Linked PDMS Material Using
PE (e.g., Bio-Renewable PE) as a Cross-Linking Material
[0025] As a prophetic example, an alkoxy-functionalized siloxane
(e.g., a methoxy-functionalized siloxane) may be mixed with a PE
cross-linker (1-20% w/w) and catalyst (DBDTL in this case,
0.1%-2.0% w/w). The mixture may be applied to molds or coated onto
a substrate and cured for times and temperatures as appropriate for
desired applications.
[0026] Thus, FIG. 2 illustrates an example of the preparation of a
cross-linked PDMS material using PE as a cross-linking material.
When the PE cross-linking material is derived from renewable
resources, the bio-renewable content of a resulting cross-linked
PDMS material may be increased.
[0027] Referring to FIG. 3, a chemical reaction diagram 300
illustrates the preparation of a cross-linked PDMS material using a
PE-derived cross-linking material (illustrated as "PE Derivate(1)"
in FIG. 3), according to one embodiment. In some cases, the
PE-derived cross-linking material of FIG. 3 may be formed from
bio-renewable PE, bio-renewable acetic acid, or a combination
thereof. In the example of FIG. 3, a mixture may be formed that
includes a PDMS material (e.g., a hydroxy-functionalized siloxane)
and PE-derived cross-linking material. The cross-linked PDMS
material illustrated in FIG. 3 may be formed via a chemical
reaction (e.g., a condensation cure reaction) of the PE-derived
cross-linking material and the PDMS material.
[0028] FIG. 3 illustrates that PE (e.g., bio-renewable PE) may be
chemically reacted with acetic acid or acetic anhydride via an
acylation reaction to form a PE-based cross-linker with multiple
acetate groups. In some cases, the acetic acid can be obtained from
renewable sources. Further, acetic anhydride may be synthesized
from bio-renewable acetic acid.
[0029] FIG. 3 illustrates an example in which all four functional
groups of a single PE-based cross-linking molecule are used as
cross-linking sites. Depending on the reaction conditions, all four
functional groups can be used to cross-link PDMS or, by controlling
the reaction conditions, catalyst loading, and stoichiometry, a
fraction of the functional groups (e.g., less than four functional
groups per PE-based molecule, on average) can be used to cross-link
PDMS. This may enable more control of the mechanical properties of
the final polymer.
Prophetic Example: Synthesis of PE-Based Cross-Linking Material Via
Esterification of PE (e.g., Bio-Renewable PE)
[0030] As a prophetic example, pentaerythritol (1 equiv.), acetic
acid (4.5-5.0 equiv.), catalytic p-toluenesulfonic acid (or other
catalysts such as sulfonic acids, sulfuric acid, phosphoric acid,
hydrogen sulfates, dihydrogen phosphates, phosphonic acid esters,
or dialkyl tin dioxides), and a suitable amount of toluene (or
other water-azeotrope forming solvents) may be added to a reaction
vessel and heated under azeotropic distillation conditions (e.g.,
refluxing using a Dean-Stark apparatus) until water is no longer
removed from the reaction. The mixture may be cooled to room
temperature, and the organic layer may be separated, rinsed with
water, dried and purified.
Prophetic Example: Formation of a Cross-Linked PDMS Material Using
PE-Based Cross-Linking Material
[0031] As a prophetic example, a Si--OH functionalized siloxane may
be blended with an acetoxy-PE cross-linker (1-50% w/w) and blended
with exclusion of moisture. The blended mixture may be stored under
moisture-free conditions. The blended mixture may be applied to
surfaces and materials and allowed to cure under atmospheric
conditions.
[0032] Thus, FIG. 3 illustrates an example of the preparation of a
cross-linked PDMS material using a PE-derived cross-linking
material. When the PE-derived cross-linking material of FIG. 3 is
derived from renewable resources, the bio-renewable content of a
resulting cross-linked PDMS material may be increased.
[0033] Referring to FIG. 4, a chemical reaction diagram 400
illustrates the preparation of a cross-linked PDMS material using a
PE-derived cross-linking material (illustrated as "PE Derivate(2)"
in FIG. 4), according to one embodiment. In some cases, the
PE-derived cross-linking material of FIG. 4 may be formed from
bio-renewable PE, bio-renewable acrylic acid, or a combination
thereof. In the example of FIG. 4, a mixture may be formed that
includes a PDMS material (e.g., a Si--CH.sub.3 functional siloxane)
and PE-derived cross-linking material. The cross-linked PDMS
material illustrated in FIG. 4 may be formed via a chemical
reaction (e.g., a radical cure reaction using a peroxide initiator)
of the PE-derived cross-linking material and the PDMS material.
[0034] FIG. 4 illustrates that PE (e.g., bio-renewable PE) may be
chemically reacted with acrylic acid via an acid (or base)
catalyzed condensation reaction to form a PE-based cross-linker
with multiple vinyl groups. In some cases, the acrylic acid can be
obtained from renewable sources.
[0035] FIG. 4 illustrates an example in which all four functional
groups of a single PE-based cross-linking molecule are used as
cross-linking sites. Depending on the reaction conditions, all four
functional groups can be used to cross-link PDMS or, by controlling
the reaction conditions, catalyst loading, and stoichiometry, a
fraction of the functional groups (e.g., less than four functional
groups per PE-based molecule, on average) can be used to cross-link
PDMS. This may enable more control of the mechanical properties of
the final polymer.
Prophetic Example: Synthesis of PE-Based Cross-Linking Material Via
Esterification of PE (e.g., Bio-Renewable PE)
[0036] As a prophetic example, pentaerythritol (1 equiv.), acrylic
acid (4.5-5.0 equiv.), catalytic p-toluenesulfonic acid (or other
catalysts such as sulfonic acids, sulfuric acid, phosphoric acid,
hydrogen sulfates, dihydrogen phosphates, phosphonic acid esters,
or dialkyl tin dioxides), and a suitable amount of toluene (or
other water-azeotrope forming solvents) may be added to a reaction
vessel and heated under azeotropic distillation conditions (e.g.,
refluxing using a Dean-Stark apparatus) until water is no longer
removed from the reaction. The mixture may be cooled to room
temperature, and the organic layer may be separated, rinsed with
water, dried and purified.
Prophetic Example: Formation of a Cross-Linked PDMS Material Using
a PE-Based Cross-Linking Material
[0037] As a prophetic example, a Si--CH.sub.3 functional siloxane
may be blended with a vinyl-PE cross-linker (1-20% w/w) and
catalyst (e.g., benzoyl peroxide, 0.2%-1.0% w/w) and mixed. The
mixture may be applied to molds or coated onto a substrate and
cured for times and temperatures (e.g., 140-160.degree. C., with a
post cure of 25-30.degree. C. higher than the initial reaction
temperature to remove volatile peroxides) as appropriate for
desired applications.
[0038] Thus, FIG. 4 illustrates another example of the preparation
of a cross-linked PDMS material using a PE-derived cross-linking
material. When the PE-derived cross-linking material of FIG. 4 is
derived from renewable resources, the bio-renewable content of a
resulting cross-linked PDMS material may be increased.
[0039] Referring to FIG. 5, a chemical reaction diagram 500
illustrates the preparation of a cross-linked PDMS material using a
PE-derived cross-linking material (illustrated as "PE Derivate(3)"
in FIG. 5), according to one embodiment. In some cases, the
PE-derived cross-linking material of FIG. 5 may be formed from
bio-renewable PE, an allyl bromide derived from a bio-renewable
allyl alcohol, or a combination thereof. In the example of FIG. 5,
a mixture may be formed that includes a PDMS material (e.g., a
hydride-functionalized siloxane) and PE-derived cross-linking
material. The cross-linked PDMS material illustrated in FIG. 5 may
be formed via a chemical reaction (e.g., an addition cure reaction
with a platinum catalyst) of the PE-derived cross-linking material
and the PDMS material. As described further herein, the PE-derived
cross-linking material illustrated in FIG. 5 may be used to
synthesize the PE-derived cross-linking material of FIG. 8.
[0040] FIG. 5 illustrates that PE (e.g., bio-renewable PE) may be
chemically reacted with allyl bromide via a substitution reaction
to form a PE-based cross-linker with multiple vinyl groups (that is
different from the PE-based cross-linker with multiple vinyl groups
shown in FIG. 4). In some cases, the allyl bromide may be
synthesized from a bio-renewable allyl alcohol.
[0041] FIG. 5 illustrates an example in which all four functional
groups of a single PE-based cross-linking molecule are used as
cross-linking sites. Depending on the reaction conditions, all four
functional groups can be used to cross-link PDMS or, by controlling
the reaction conditions, catalyst loading, and stoichiometry, a
fraction of the functional groups (e.g., less than four functional
groups per PE-based molecule, on average) can be used to cross-link
PDMS. This may enable more control of the mechanical properties of
the final polymer.
Prophetic Example: Synthesis of PE-Based Cross-Linking Material
[0042] As a prophetic example, tetrakis(allyl)pentaerythritol ether
may be synthesized by adding pentaerythritol (1 equiv.) and
dimethylsulfoxide (11 equiv.) to a reaction vessel equipped with a
condenser and a mechanical stirrer. The vessel may be heated to
about 80.degree. C., and sodium oxide (4.4 equiv.) may be added to
the reaction mixture, causing the reaction temperature to increase
slightly. Once the temperature has returned to 80.degree. C., the
reaction vessel may be purged with nitrogen, and allyl chloride
(4.4 equiv.) may be added slowly to the reaction mixture as to
maintain a temperature below about 90.degree. C. Upon completion of
the addition, the reaction mixture may be stirred at about
85.degree. C. for about 2 hours. The reaction mixture may be
diluted with water, cooled and extracted with diethyl ether. The
organic solvents may be removed in vacuo, and the product may be
purified by distillation or other techniques.
Prophetic Example: Formation of a Cross-Linked PDMS Material Using
a PE-Based Cross-Linking Material
[0043] As a prophetic example, a hydride-functional siloxane may be
blended with a vinyl-PE cross-linker (1-20% w/w) and Pt catalyst
and mixed. An addition cure reaction via hydrosilation may be
performed on the mixture.
[0044] Thus, FIG. 5 illustrates another example of the preparation
of a cross-linked PDMS material using a PE-derived cross-linking
material. When the PE-derived cross-linking material of FIG. 5 is
derived from renewable resources, the bio-renewable content of a
resulting cross-linked PDMS material may be increased.
[0045] Referring to FIG. 6, a chemical reaction diagram 600
illustrates the preparation of a cross-linked PDMS material using
the PE-derived cross-linking material of FIG. 5, according to one
embodiment. In the example of FIG. 6, a mixture may be formed that
includes a PDMS material (e.g., a Si--CH.sub.3 functional siloxane)
and PE-derived cross-linking material. The cross-linked PDMS
material illustrated in FIG. 6 may be formed via a chemical
reaction (e.g., an addition/peroxide cure reaction) of the
PE-derived cross-linking material and the PDMS material.
[0046] FIG. 6 illustrates an example in which all four functional
groups of a single PE-based cross-linking molecule are used as
cross-linking sites. Depending on the reaction conditions, all four
functional groups can be used to cross-link PDMS or, by controlling
the reaction conditions, catalyst loading, and stoichiometry, a
fraction of the functional groups (e.g., less than four functional
groups per PE-based molecule, on average) can be used to cross-link
PDMS. This may enable more control of the mechanical properties of
the final polymer.
Prophetic Example: Formation of a Cross-Linked PDMS Material Using
a PE-Based Cross-Linking Material
[0047] As a prophetic example, a Si--CH.sub.3 functional siloxane
may be blended with vinyl-PE cross-linker (1-20% w/w) and catalyst
(e.g., benzoyl peroxide, 0.2%-1.0% w/w) and mixed. The mixture may
be applied to molds or coated onto a substrate and cured for times
and temperatures (e.g., 140-160.degree. C., with a post cure of
25-30.degree. C. higher than the initial reaction temperature to
remove volatile peroxides) as appropriate for desired
applications.
[0048] Thus, FIG. 6 illustrates another example of the preparation
of a cross-linked PDMS material using the PE-derived cross-linking
material of FIG. 5. When the PE-derived cross-linking material is
derived from renewable resources, the bio-renewable content of a
resulting cross-linked PDMS material may be increased.
[0049] Referring to FIG. 7, a chemical reaction diagram 700
illustrates the preparation of a cross-linked PDMS material using a
PE-derived cross-linking material (illustrated as "PE Derivate(4)"
in FIG. 7), according to one embodiment. In some cases, the
PE-derived cross-linking material of FIG. 6 may be formed from
bio-renewable PE, a mercaptoic acid derived from bio-renewable
acrylic acid, or a combination thereof. In the example of FIG. 7, a
mixture may be formed that includes a PDMS material (e.g., a
vinyl-functionalized siloxane) and PE-derived cross-linking
material. The cross-linked PDMS material illustrated in FIG. 7 may
be formed via a chemical reaction (e.g., a thiol-ene cure reaction)
of the PE-derived cross-linking material and the PDMS material.
[0050] FIG. 7 illustrates that PE (e.g., bio-renewable PE) may be
chemically reacted with ethyl mercaptoacetic acid via a
condensation reaction (acid/base promoted) to synthesize a
cross-linker with multiple thiol (or mercapto) groups. In some
case, the ethyl mercaptoic acid can be synthesized from
bio-renewable acrylic acid via subsequent halogenation and
substitution reactions.
[0051] FIG. 7 illustrates an example in which all four functional
groups of a single PE-based cross-linking molecule are used as
cross-linking sites. Depending on the reaction conditions, all four
functional groups can be used to cross-link PDMS or, by controlling
the reaction conditions, catalyst loading, and stoichiometry, a
fraction of the functional groups (e.g., less than four functional
groups per PE-based molecule, on average) can be used to cross-link
PDMS. This may enable more control of the mechanical properties of
the final polymer.
Prophetic Example: Synthesis of PE-Based Cross-Linking Material Via
Esterification of PE (e.g., Bio-Renewable PE)
[0052] As a prophetic example, pentaerythritol (1 equiv.),
3-mercaptopropionic acid (4.5-5.0 equiv.), catalytic
p-toluenesulfonic acid (or other catalysts such as sulfonic acids,
sulfuric acid, phosphoric acid, hydrogen sulfates, dihydrogen
phosphates, phosphonic acid esters, or dialkyl tin dioxides), and a
suitable amount of toluene (or other water-azeotrope forming
solvents) may be added to a reaction vessel and heated under
azeotropic distillation conditions (e.g., refluxing using a
Dean-Stark apparatus) until water is no longer removed from the
reaction. The mixture may be cooled to room temperature, and the
organic layer may be separated, rinsed with water, dried and
purified.
Prophetic Example: Formation of a Cross-Linked PDMS Material Using
a PE-Based Cross-Linking Material
[0053] As a prophetic example of a thiol-ene cure of a
thiol-functionalized PE with a vinyl-siloxane, a thiol-PE
cross-linker (2-6% w/w) may be mixed with a vinyl-functionalized
siloxane. The mixture may include a radical initiator, such as a
Micheler's ketone, an alpha-amino-ketone, an alpha-hydroxy-ketone,
a benzyldimethyl ketal, or benzophenone (among other alternatives).
The mixture may be applied to molds or coated onto a substrate and
cured under UV light at a time and temperature suitable to the
included radical initiators as appropriate for desired
applications.
[0054] Thus, FIG. 7 illustrates another example of the preparation
of a cross-linked PDMS material using a PE-derived cross-linking
material. When the PE-derived cross-linking material of FIG. 7 is
derived from renewable resources, the bio-renewable content of a
resulting cross-linked PDMS material may be increased.
[0055] Referring to FIG. 8, a chemical reaction diagram 800
illustrates the preparation of a cross-linked PDMS material using a
PE-derived cross-linking material (illustrated as "PE Derivate(5)"
in FIG. 8), according to one embodiment. In some cases, the
PE-derived cross-linking material of FIG. 8 may be formed from
bio-renewable PE, a mercaptoic acid derived from bio-renewable
acrylic acid, an allyl bromide derived from a bio-renewable allyl
alcohol (as described herein with respect to FIG. 5), or a
combination thereof. In the example of FIG. 8, a mixture may be
formed that includes a PDMS material (e.g., a vinyl-functionalized
siloxane) and PE-derived cross-linking material. The cross-linked
PDMS material illustrated in FIG. 8 may be formed via a chemical
reaction (e.g., a thiol-ene cure reaction) of the PE-derived
cross-linking material and the PDMS material.
[0056] FIG. 8 illustrates that PE (e.g., bio-renewable PE) may be
chemically reacted with an allyl bromide (see FIGS. 5 and 6) via a
substitution reaction, followed by halogenation and thiol
substitution reactions (similar to FIG. 7) to form a cross-linker
with multiple thiol (mercapto) groups.
[0057] FIG. 8 illustrates an example in which all four functional
groups of a single PE-based cross-linking molecule are used as
cross-linking sites. Depending on the reaction conditions, all four
functional groups can be used to cross-link PDMS or, by controlling
the reaction conditions, catalyst loading, and stoichiometry, a
fraction of the functional groups (e.g., less than four functional
groups per PE-based molecule, on average) can be used to cross-link
PDMS. This may enable more control of the mechanical properties of
the final polymer.
Prophetic Example: Synthesis of PE-Based Cross-Linking Material
[0058] As a prophetic example,
tetrakis(propanethiol)pentaerythritol may be synthesized using
tetrakis(allyl)pentaerythritol ether (illustrated in FIGS. 5 and
6). To a stirred solution of tetrakis(allyl)pentaerythritol ether
(1 equiv.), in benzene or DCM (or another suitable solvent for
radical reactions), a catalytic amount of benzoyl peroxide (BPO)
(or other radical initiators, such as azobisisobutyronitrile
(AIBN)), and hydrobromic acid (>4 equiv.) may be added. The
reaction may be heated to reflux (optionally activated by UV light)
until complete. The reaction may be quenched with water, and the
organic layer may be separated and dried, and the solvents may be
removed in vacuo. The product may be purified by vacuum
distillation or by other techniques.
[0059] To a stirred solution of
tetrakis(bromopropane)pentaerythritol ether (1 equiv., the product
from the previous reaction) in ethanol is added thiourea (>4
equiv.). The reaction mixture may be heated to reflux and stirred
for about 6-24 hours or until complete conversion. The reaction may
be cooled slightly, and the ethanol may be removed under reduced
pressure. To the resulting salt, an excess amount of a solution of
aqueous sodium hydroxide (10% w/w) may be added. The solution may
be refluxed for about 3 hours or until the reaction is complete.
The reaction mixture may be neutralized with dilute hydrochloric
acid, extracted with diethyl ether, and the solvents may be removed
in vacuo. The product may be purified by vacuum distillation or by
other techniques.
Prophetic Example: Formation of a Cross-Linked PDMS Material Using
a PE-Based Cross-Linking Material
[0060] As a prophetic example of a thiol-ene cure of a
thiol-functionalized PE with a vinyl-functionalized siloxane, a
thiol-PE cross-linker (2-6% w/w) may be mixed with a
vinyl-functionalized siloxane. The mixture may include a radical
initiator, such as a Micheler's ketone, an alpha-amino-ketone, an
alpha-hydroxy-ketone, a benzyldimethyl ketal, or benzophenone
(among other alternatives). The mixture may be applied to molds or
coated onto a substrate and cured under UV light at a time and
temperature suitable to the included radical initiators as
appropriate for desired applications.
[0061] Thus, FIG. 8 illustrates another example of the preparation
of a cross-linked PDMS material using a PE-derived cross-linking
material. When the PE-derived cross-linking material of FIG. 8 is
derived from renewable resources, the bio-renewable content of a
resulting cross-linked PDMS material may be increased.
[0062] The previous description of the disclosed embodiments is
provided to enable any person skilled in the art to make or use the
disclosed embodiments. Various modifications to these embodiments
will be readily apparent to those skilled in the art, and the
generic principles defined herein may be applied to other
embodiments without departing from the scope of the disclosure.
Thus, the present disclosure is not intended to be limited to the
embodiments shown herein but is to be accorded the widest scope
possible consistent with the principles and features as defined by
the following claims.
* * * * *